Raman optical activity spectra of chiral transition metal complexes

We present calculated vibrational Raman optical activity (ROA) spectra for the transition metal complexes Λ-tris(acetylacetonato)cobalt(III), Λ-tris(acetylacetonato)rhodium(III), dichloro-(6R,7S,9S,11S-(−)-sparteine)zinc(II) and Δ(δδδ)-tris(ethylenediaminato)cobalt(III). For this study, it was necessary to benefit from density-fitting techniques to a large extent. Necessary implementations are described and the gauge origin problem is addressed. The importance of the electric-dipole-electric-quadrupole polarizability tensor for ROA intensity differences is investigated and found to be small, especially at lower wavenumbers where no C-H stretching vibrations occur. Furthermore, the basis set and density functional dependence is examined.